JP2003162205A - Photocurable resin composition, sheet, transfer foil, fine concavo-convex pattern forming method, and optical article - Google Patents

Abstract

(57) [PROBLEMS] To provide a photocurable resin composition capable of forming an accurate fine concavo-convex pattern even when embossed at a relatively low temperature in a short time, and to prevent blocking when used as a wound body, and fine concavo-convex A pattern forming method, a wound body, and an optical article are provided. SOLUTION: As an essential component, a binder resin containing (1) an acrylic resin and (2) a urethane acrylate resin and / or a polyester acrylate resin having a photopolymerizable functional group, and (3) film forming properties of the binder resin. It is a photocurable resin composition having a reduced softening temperature, which contains an organic metal coupling agent for increasing the viscosity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable resin composition suitable for forming a fine uneven pattern on a surface by embossing, a fine uneven pattern forming method using the resin composition, and an optical article. , And more specifically, a photocurable resin composition and a fine uneven pattern forming method capable of lowering the softening start temperature of a binder resin having a photopolymerizable functional group by an additive, and an optical article, for example, An optical element for controlling at least one of optical phenomena such as reflection, transmission, scattering, polarization, focusing, and interference, which has a fine uneven pattern formed using the photocurable resin composition on its surface, and more specifically , Relief type hologram,
The present invention relates to an optical article such as a diffraction grating, an antireflection film, a scattering plate and a reflection plate, and formation of a fine concavo-convex pattern thereof.

[0002]

2. Description of the Related Art Conventionally, a photocurable resin composition (paint) is
For example, a layer of a photocurable resin composition is formed by coating on a film-shaped support such as a polyester film, and various fine uneven patterns are applied to the layer of the photocurable resin composition, and then ultraviolet rays or electrons are applied. Exposure by irradiating ionizing radiation such as rays,
A method is used in which the resin layer is cured and metal vapor deposition or a layer having a different refractive index is laminated on the cured fine concavo-convex pattern surface to form a diffraction grating or a relief hologram.

As a method of applying the fine concavo-convex pattern, for example, in the case of forming a relief hologram,
A press stamper (hereinafter simply referred to as a press stamper) prepared from a master hologram on which a desired fine concavo-convex pattern is formed is prepared, and the press stamper is superposed on the layer of the photocurable resin composition and pressed ( The embossing process) is performed to transfer the fine concavo-convex pattern of the press stamper to the resin layer, and the state is exposed to light to cure the resin layer to fix the fine concavo-convex pattern. When a large number of relief holograms are formed in this way, a large number of embossing processes are performed with a single press stamper.

[0004]

When embossing is applied to a photocurable resin composition, it is necessary that the resin composition be soft. However, a photocurable resin composition that is easily softened at room temperature is used to form a layer of the photocurable resin composition on a film-shaped support, and the product obtained by winding the film is stuck or stuck. Since blocking easily occurs, there is a disadvantage that it cannot be stored. Therefore, it is desirable to use a photocurable resin composition that is hard to soften at room temperature, that is, hard.

On the other hand, when a photocurable resin composition which is hard to be softened at room temperature is used, heat is not sufficiently transferred to the layer of the photocurable resin composition during heating during embossing, so that the fine uneven pattern of the plate is used. May not be accurately formed on the surface of the layer of the photocurable resin composition, in order to impart a fine uneven pattern to such a resin composition, further increase the temperature,
And / or it is necessary to slow down the supply speed of the support, but in this case, by increasing the temperature, the plate is damaged, the film-shaped support is deteriorated, and the fine uneven pattern application speed is slowed down. This is not preferable because it lowers the production efficiency.

Therefore, according to the present invention, even if embossed at a relatively low temperature for a relatively short time, a finer uneven pattern can be formed more accurately than in the case of using a conventional photocurable resin composition.
Moreover, a photocurable resin capable of improving the duplication speed of the fine concavo-convex pattern and capable of preventing the occurrence of blocking at room temperature in a sheet such as a roll having a layer of the photocurable resin composition formed on a support. It is an object of the present invention to provide a composition, a method for forming a fine concavo-convex pattern using the resin composition, a sheet such as a winding body, a transfer foil, and an optical article.

[0007]

The photocurable resin composition of the present invention for solving the above-mentioned problems has (1) an acrylic resin and (2) a urethane having a photopolymerizable functional group as essential components. A photocurable resin composition comprising a binder resin containing an acrylate resin and / or a polyester acrylate resin, and (3) an organometallic coupling agent for enhancing the film forming property of the binder resin,
The photocurable resin composition is used for forming a fine concavo-convex pattern of an optical article.

The film-shaped support coated with the photocurable resin composition of the present invention is characterized in that blocking is prevented by the organometallic coupling agent in the uncured state before exposure. In addition, since the surface of the sheet in which the layer of the photocurable resin composition of the present invention is formed on the film-like support becomes smooth, the duplication speed in the fine concavo-convex pattern forming step is increased.

The photocurable resin composition of the present invention coated on a film-like support and then cured by exposure to a binder resin has improved heat resistance and durability. Further, in the case of a layer before and after contact with the cured resin layer, for example, in the case of a transfer foil for forming a relief hologram, the adhesion with the metal vapor deposition layer is improved and the transferability becomes good.

In the photocurable resin composition of the present invention, the acrylic resin of (1) above, which does not contain the organometallic coupling agent, and the urethane acrylate resin having a photopolymerizable functional group of (2) above, Most preferably, when the average (Ra) of the surface roughness of the coating film when coated with a resin mixed with a polyester acrylate resin is preferably 1.0 nm or more, more preferably 3.0 nm or more. When it is 5.0 nm or more, when the organometallic coupling agent is contained in the photocurable resin composition, each of the above effects becomes remarkable.

The acrylic resin used in the present invention is necessary for exhibiting transparency and strength as an optical material and imparting thermoplasticity when the uneven pattern is formed by hot pressing. The photopolymerizable urethane acrylate and / or polyester acrylate used in the present invention is for the purpose of imparting strength, heat resistance, scratch resistance, water resistance and chemical resistance in addition to the properties of the acrylic resin. ,
It is added to increase the crosslink density and to impart photopolymerizability.

When the photocurable resin composition does not contain an organometallic coupling agent, a resin obtained by mixing an acrylic resin and a photopolymerizable urethane acrylate and / or polyester acrylate is applied to form a coating film. When the formed sheets are piled up, for example, a rolled-up rolled body is apt to stick and cause blocking, but the photocurable resin composition of the present invention has an organometallic cup. Since the sheet contains a ring agent, the sheet produced as described above using the photocurable resin composition of the present invention can prevent blocking from occurring.

Regarding the action of the organometallic coupling agent in the present invention for preventing the blocking as described above, it is presumed that the binder resin and the organometallic coupling agent interact with each other, and a polymer component having a large molecular chain and an oligomer component having a small molecular weight are produced. It is thought that this is because the organometallic coupling agent acts as a binding component to bind the amides and prevents the oligomer component from melting in a low temperature environment.

In the present invention, the addition of the organometallic coupling agent to the photocurable resin composition has the effect of smoothing the surface of the coating film before the fine uneven pattern forming treatment. It is considered that this effect is due to the fact that the organometallic coupling agent enhances the compatibility with the poorly compatible resin and suppresses the non-uniformity of the coating film.

The reason why the duplication speed is increased in the present invention is that the surface of the layer of the photocurable resin composition formed on the film-shaped support is obtained by incorporating the organometallic coupling agent into the photocurable resin composition. Is smooth, the hardness is uniform and the stamper is easy to apply, and
It is considered that this is because the photocurable resin composition containing the organometallic coupling agent has a lower softening start temperature, which makes it possible to speed up the process of forming the fine concavo-convex pattern.

By utilizing such characteristics of the photocurable resin composition of the present invention, a layer of the photocurable resin composition of the present invention formed on a film-shaped support is embossed on the surface with an embossing plate. After processing, it is possible to remove the sheet with the photo-curable resin composition layer from the embossing plate, and then expose it to obtain a sheet with the resin-cured layer having a fine uneven pattern on the surface. Becomes Therefore, in the formation of an accurate fine uneven pattern, the unevenness formation and the exposure can be performed by using the photocurable resin composition of the present invention without using a large-scale device designed to simultaneously perform the uneven formation and the exposure. There is a feature that the devices arranged separately can be used.

This process is employed in comparison with a process in which embossing and exposure are carried out almost at the same time, and thereafter, a sheet having a layer of a cured resin material having a fine uneven pattern on the surface is peeled from the embossing plate to remove the resin. Since it can be peeled off from the embossing plate in a cured state, it is possible to suppress scratches on the surface of the resin cured product, which are likely to occur when the sheet on which the resin cured product layer is formed is peeled off. Further, the exposure to the layer of the photocurable resin composition, without performing through the film-like support,
Since it can be directly applied to the layer of the photocurable resin composition, the exposure efficiency is improved.

The lowering of the softening initiation temperature in the photocurable resin composition of the present invention means that the organometallic coupling agent is contained when determined from the value of the dynamic storage elastic modulus determined by the dynamic viscoelasticity measuring method. It is a softening start temperature lower than that of the case where it is not applied, and is desirably at least 2 ° C. or more.

The dynamic viscoelasticity measuring method used for evaluating the decrease in the softening start temperature is performed as follows. The resin material is dried at room temperature to volatilize the solvent, and then vacuum dried at room temperature. The measurement is performed with a dynamic viscoelasticity measuring device. As the measuring device, for example, Rheogel-E400 (manufactured by UBM) can be used. Slit part of liquid shear jig of measuring device (gap 0.8mm, size 20x
20 mm) is packed with the above dried sample. The measurement conditions are
The basic measurement frequency is 10Hz, the distorted waveform is a sine wave,
Strain control is 0.5 μm, temperature range is room temperature to 150 ° C.,
The temperature rising rate is measured at 3 ° C./mim. The point at which the measured value of the dynamic storage elastic modulus is 3% or more lower than the value at 30 ° C. is defined as the softening start temperature.

The photocurable resin composition of the present invention comprises a non-polymerizable transparent resin, a monofunctional or polyfunctional monomer and / or a monofunctional or polyfunctional oligomer, a release agent, an organic metal as an optional component other than the above components. Coupling agent, photopolymerization initiator,
A polymerization inhibitor and the like may be contained if necessary.

The sheet of the present invention is characterized in that the photocurable resin composition of the present invention is applied to a film-like support and dried or not dried. Generally, it is a continuous sheet and is wound, but it may be in the form of a single sheet. Since the sheet of the present invention contains the organometallic coupling agent in the layer of the uncured photocurable resin composition, blocking is prevented even during storage.

The method for forming a fine concavo-convex pattern of the present invention is
The photocurable resin composition of the present invention is applied to the surface of a film-like support to form a layer of the photocurable resin composition, and then the surface of the layer of the photocurable resin composition is embossed. And the exposure is performed almost simultaneously to form a cured resin layer having a fine concavo-convex pattern formed on the surface. Another method for forming a fine concavo-convex pattern of the present invention is to form a layer of the photocurable resin composition by applying the photocurable resin composition of the present invention to the surface of a film-like support, The surface of the layer of the functional resin composition is embossed, and then exposed and cured.

In another method of forming the fine concavo-convex pattern of the present invention, it is also possible to form using the previously manufactured sheet. That is, taking the case where the sheet is a roll as an example, the step of storing the roll, embossing and exposing the surface of the layer of the photocurable resin composition on the film-like support unwound from the roll. May be performed almost simultaneously to form a cured resin layer having a fine concavo-convex pattern formed on the surface. Another method for forming a fine concavo-convex pattern of the present invention using a winding body is that a fine concavo-convex pattern is formed after embossing the surface of the layer of the photocurable resin composition in the winding body (embossing step). A fine uneven pattern may be formed by exposing the layer of the photocurable resin composition to light (exposure step) to cure the photocurable resin layer.

The method for forming a fine concavo-convex pattern of the present invention is
Since the photocurable resin composition is used, as described above, the fine concavo-convex pattern forming process can be performed at a relatively low temperature and at a high speed.

In the method for forming a fine concavo-convex pattern of the present invention, the heating temperature at the time of embossing capable of accurately forming concavities and convexities is related to the supply speed of the film-shaped support on which the layer of the photocurable resin composition is formed. Determined by Also, since the heat resistant temperature varies depending on the material of the film-shaped support,
It is necessary to appropriately set the heating temperature and the supply speed of the film-shaped support in consideration of the material.

When the exposure step is performed after the step of forming a fine concavo-convex pattern, light can be directly irradiated from the layer side of the photocurable resin composition in a state of being peeled off from the embossing device. On the other hand, in the present invention, the fine concavo-convex pattern forming step and the exposing step can be performed almost simultaneously. However, when the exposure step is performed almost simultaneously with the fine concavo-convex pattern forming step, the film support is transmitted through the film support to perform the exposure, and therefore the film support is deteriorated by light such as ultraviolet rays. Or the light is absorbed by the film-like support, and the light irradiation is not efficient. Also used in the unevenness forming step,
For example, when the press stamper of the embossing roller is made of resin, the light such as ultraviolet rays to be irradiated may deteriorate the press stamper.

The optical article of the present invention is characterized by comprising a cured resin layer formed by using the above-mentioned photocurable resin composition and having a fine uneven pattern on the surface. The optical article of the present invention may be formed using a sheet, preferably a winding body, in which a layer of the uncured photocurable resin composition is formed on a film-shaped support.

The optical article provided with the cured resin layer having the fine uneven pattern structure on the surface of the present invention is an optical element for controlling at least one of optical phenomena such as reflection, transmission, scattering, polarization, focusing and interference. , Specifically, relief type hologram,
It can be an optical article such as a diffraction grating, an antireflection film, a scattering plate, or a reflection plate.

The optical article provided with a cured resin layer having a fine relief pattern structure on its surface according to the present invention optically records and / or records information on the fine relief pattern structure according to a known method.
Or optical articles that can be read (information recording element)
Can be

In the transfer foil of the present invention, the photocurable resin composition is applied to a film-shaped support through a release layer to form a layer of the photocurable resin composition. It is characterized in that a material layer, a layer having a different refractive index, and an adhesive layer are formed in this order.

The method for producing an optical article of the present invention using a transfer foil is (1) photocuring by applying the photocurable resin composition of the present invention to a film-like support through a release layer. A layer of a thermosetting resin composition is formed, and (2) embossing and exposure are performed almost at the same time to cure the layer of the photocurable resin composition to form a fine uneven pattern on the surface, (3)
Further, a layer having a refractive index different from that of the photocurable resin composition layer is formed, and (4) an adhesive layer is further formed as a transfer foil, and (5) the obtained transfer foil is transferred to a transfer target. It is characterized by doing. That is, the film-like support is peeled off at the part of the peeling layer, so that the film-like support is transferred to the transfer target to obtain an optical article.

Another aspect of the method for producing an optical article of the present invention using a transfer foil is (1) applying the photocurable resin composition of the present invention to a film-like support through a release layer. To form a layer of the photocurable resin composition, and (2) after embossing, the layer of the photocurable resin composition is cured by exposure to form a fine uneven pattern on the surface,
(3) Further, a layer having a refractive index different from that of the photocurable resin composition layer is formed, (4) Further, an adhesive layer is formed as a transfer foil, and (5) the obtained transfer foil is transferred. It is characterized by being transferred to the body.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION The photocurable resin composition and the method for forming a fine concavo-convex pattern of the present invention will be further described with reference to preferred embodiments.

Organometallic Coupling Agent The organometallic coupling agent used in the present invention is added to form a layer of the photocurable resin composition and prevent blocking when wound into a wound body. It Further, the organometallic coupling agent is added in order to lower the softening temperature of the photocurable resin composition and speed up the process of forming the fine concavo-convex pattern.

The organometallic coupling agent is preferably 0.1 to 20% by weight based on the total solid content of the photocurable resin composition. The content of the organometallic coupling agent is 0.
If it is less than 1% by weight, there is no effect of preventing blocking. If it exceeds 20% by weight, the storage stability of the photocurable resin composition and the roll having the photocurable resin composition layer formed thereon is impaired.

Examples of the organometallic coupling agent include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent. Particularly, those having a good effect of smoothing the film surface are An aluminum coupling agent may be used.

For a material having a Ra value of 1 nm or less and forming a smooth film surface, the smoothing effect of the organometallic coupling agent is considerably small. However, when an aluminum coupling agent having an alkoxy group is added, the effect of making a smoother surface is confirmed. This effect is prominent when a combination of acrylic resin and urethane acrylate resin is selected as the binder.

Suitable silane coupling agents include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and other vinylsilanes; γ-methacryloxy, γ-methacryloxypropyltrimethoxysilane. ,
Acrylic silanes such as γ-methacryloxypropylmethyldimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane Epoxy silane such as N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. Aminosilanes can be used. As other silane coupling agents, γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane and the like can be used.

The titanium coupling agent is, for example,
Isopropyltriisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyl) Oxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacrylic titanate, Isopropyl tri (dioctyl phosphate) Titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

Examples of zirconium coupling agents include tetra-n-propoxyzirconium and tetra-n-propoxyzirconium.
Examples thereof include butoxy zirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis (ethylacetoacetate).

Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), Alkyl acetoacetate aluminum diisopropylate,
Aluminum monoacetyl acetonate bis (ethyl acetoacetate), aluminum tris (acetyl acetoacetate), etc. can be mentioned. Among the aluminum coupling agents, those having an alkoxy group are mentioned as particularly excellent in the effect of smoothing the film surface. However, some of the alkoxy groups are preferably chelated because the alkoxy groups are highly reactive and the stability of the composition decreases.

Binder Resin Having Photopolymerizable Functional Group In the present invention, the binder resin having a photopolymerizable functional group has at least one binder resin having a polystyrene-reduced weight average molecular weight of 5,000 to 600,000.
It is desirable that it is in the range of, and more preferably 5,0
00-300,000, most preferably 5,000-
It is 200,000. If the polystyrene-equivalent weight average molecular weight is less than 5,000, the tackiness of the surface cannot be suppressed, which is not preferable, and as the polystyrene-equivalent weight average molecular weight increases, the fine unevenness pattern of the optical article formed by stamping is formed. It is preferable in that the stability becomes high, but if it exceeds 600,000, the softening start temperature of the binder resin becomes too high and the suitability for thermal processing is deteriorated, which is not preferable. The binder resin having a molecular weight in the above range preferably accounts for 20% by weight or more of the entire binder resin.

As an optional component, another binder resin component having a molecular weight outside the above range may be added to the essential binder resin component, and the other binder resin component has a polystyrene reduced weight average molecular weight of less than 5,000. You may use the thing. A binder resin having a molecular weight of less than 5,000 may be added as necessary for the purpose of lowering the softening start temperature of the resin, but it may occur in a roll formed using the photocurable resin composition. Considering prevention of tack, the ratio of the other binder resin components is preferably 80% by weight or less based on the whole binder resin.

Acrylic Resin The acrylic resin used as the binder resin component in the present invention is used as a thermoplastic resin for molding the transparency, strength and uneven pattern as an optical material by hot pressing.

Any polymer can be used as long as it is a polymer obtained by polymerizing a general (meth) acrylate monomer or a polymer obtained by copolymerizing a (meth) acrylate monomer and a vinyl monomer. For example, (meth) acrylic acid, methyl (meth) acrylate, (meth)
Ethyl acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, dimethylacrylamide, dimethyl Examples thereof include polymers obtained by polymerizing aminoethyl (meth) acrylate and the like, but are not limited thereto.

In the present specification, "... (meth) acrylic acid" means "... acrylic acid or ... Methacrylic acid".
"... (meth) acrylate" means "... acrylate,
Or ... "methacrylate" and "... (meth) acryloyl" means "... acryloyl or ... methacryloyl"
Mean respectively.

In order to form the fine concavo-convex pattern, a press stamper on which the fine concavo-convex pattern is formed is used.
After the resin layer is embossed, a monomer having a group that imparts releasability can be copolymerized in order to prevent the resin layer from migrating to the press stamper. For example, a silicone oil (resin) having a polymerizable double bond such as (meth) acryloyl-modified silicone oil (resin) or vinyl-modified silicone oil (resin), or silicon such as γ- (meth) alkoxypropyltrimethoxysilane is contained. Monomer, 2- (perfluoro-7-methyloctyl)
Examples include fluorine-containing monomers such as ethyl (meth) acrylate.

In order to have strength, heat resistance, scratch resistance, water resistance, chemical resistance as an optical material, and flexibility and thermoplasticity for processing, especially cyclohexyl (meth) acrylate, Bulky structures such as dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, styrene, α-methylstyrene, 4-vinylpyridine, acryloylmorpholine, vinylpyrrolidone and vinylcaprolactone, The thing which copolymerized the monomer which has a cyclic structure etc. is suitable.

Among them, as a preferable example, it is obtained by copolymerizing 20 to 90 mol of methyl methacrylate, 0 to 80 mol of isobornyl methacrylate, 0 to 50 mol of methacrylic acid and 10 to 80 mol of 2-hydroxymethyl methacrylate. Preferred are acrylic copolymers.

However, when such a structure having releasability, a bulky structure, a cyclic structure, etc. is introduced,
It becomes difficult to dissolve in a diluting solvent for coating, compatibility with urethane acrylate and polyester acrylate mixed for the purpose of increasing crosslink density and imparting flexibility deteriorates, and when forming a resin layer, coating The density of the film surface becomes high. As a result, the transparency of the resin may be lost, or the heat processability for forming the uneven pattern may be deteriorated. As described above in such a case, the present invention has an acrylic resin and a photopolymerizable functional group by adding an organometallic coupling agent, particularly preferably an aluminum coupling agent, to the photocurable resin composition. The compatibility with the urethane acrylate resin and / or the polyester acrylate resin is enhanced, and the coating film surface formed by the photocurable resin composition is made smooth.

Urethane acrylate having photopolymerizable functional group
Resin and / or polyester acrylate resin The urethane acrylate resin and / or polyester acrylate resin used as the binder resin component in the present invention has strength, heat resistance, scratch resistance, water resistance and chemical resistance of the acrylic resin. It is added to further enhance the properties, to increase the crosslink density, and to impart photopolymerizability. Further, it is possible to add processing flexibility.

Any urethane acrylate can be used as long as it has a urethane bond and a photopolymerizable (meth) acryloyl group in the molecule. Among urethane acrylates, an isocyanate compound having two or more isocyanate groups, a compound having two or more hydroxyl groups, one or more hydroxyl groups and one or more (meth)
Urethane acrylate obtained by reacting a compound having an acryloyl group, or an isocyanate compound having two or more isocyanate groups, and a compound having two or more hydroxyl groups and one or more (meth) acryloyl groups The resulting urethane acrylate is preferred.

Particularly preferred is a reaction product of an isocyanate compound having a melting point of 40 ° C. or higher, particularly a trimer of isophorone diisocyanate, and a compound having a (meth) acryloyl group and capable of reacting with an isocyanate group. Urethane acrylates disclosed in JP 2001-329031 A are preferred.

Examples of the isocyanate compound having two or more isocyanate groups used for the synthesis of urethane acrylate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and 4,4 '.
-Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4-diphenylene isocyanate, isophorone diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane , 1,3-bis (α, α-dimethylisocyanate methyl) benzene, trimethylhexamethylene diisocyanate, hydrogenated xylylene diisocyanate and the like. These may be used alone or in combination of two or more.

Examples of the compound having two or more hydroxyl groups used in the synthesis of urethane acrylate include 1,3
-Butanediol, 1,4-butanediol, trimethylolethane, trimethylolpropane, ditrimethylolethane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, diglycerol, glycerin, and many other polysiloxane polyols , Poly (oxyalkylene) polyols, polyester polyols, polyether polyols, polyether polyester polyols,
Examples thereof include polyolefin polyols, poly (alkyl acrylate) polyols, and polycarbonate polyols.

Examples of the compound having at least one hydroxyl group and at least one (meth) acryloyl group used for the synthesis of urethane acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate may be mentioned.

Any polyester acrylate can be used as long as it has an ester bond and a photopolymerizable (meth) acryloyl group in the molecule. Among the polyester acrylates, polyester acrylates obtained by further reacting a compound having two or more hydroxyl groups or a polyester compound synthesized from a cyclic ester compound and a polybasic acid with a compound having a (meth) acryloyl group are preferable.

As the compound having two or more hydroxyl groups used for synthesizing the polyester acrylate, the same compounds as those used for synthesizing the urethane acrylate can be used.

Examples of the cyclic ester compound used in the synthesis of polyester acrylate include ε-caprolactone, δ-valerolactone, γ-butyrolactone and γ-
Examples thereof include a lactone compound such as valerolactone, a derivative thereof, or an addition reaction product of the lactone compound and an epoxy compound such as glycidyl methacrylate.

Examples of the polybasic acid used in the synthesis of the polyester acrylate include saturated polybasic acids such as adipic acid, succinic acid and sebacic acid; unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid. An aromatic polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid or trimellitic acid may be mentioned.

The urethane-modified acrylic resin, urethane acrylate resin, and polyester acrylate resin described above are, after curing, transparency, strength, scratch resistance, heat resistance, water resistance, chemical resistance, and adhesion to a film-like support. , Flexibility, and excellent followability to flexion and expansion and contraction of the film-like support, and sufficient film-forming property, flexibility and creeping property capable of forming a film on the film-like support and imprinting an uneven pattern with a stamper. Since it has, it is preferably used in the present invention.

Photopolymerizable monofunctional or polyfunctional monomers
-, Monofunctional or polyfunctional oligomer In order to reduce the viscosity of the photocurable resin composition of the present invention, and to adjust the flexibility and crosslink density of the resin layer obtained after curing, the photocurable resin composition of the present invention A monofunctional or polyfunctional monomer, a monofunctional oligomer or a polyfunctional oligomer, or a usual thermoplastic resin may be added to the product. For example, monofunctional tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyrrolidone, (meth) acryloyloxyethyl succinate, (meth) acryloyloxyethyl phthalate, and other mono (meth) acrylates, isobornyl (meth) ) Acrylate, cyclohexynyl (meth) acrylate,
Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate; when bifunctional or higher, when classified by skeleton structure, polyol (meth) acrylate (epoxy-modified polyol (meth) acrylate, lactone-modified polyol (meth) acrylate, etc. ), Polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, other polybutadiene type, isocyanuric acid type, hydantoin type, melamine type, phosphoric acid type, imide type, phosphazene type, cardo type, bisphenol type , Polyphenyl (meth) acrylates having a skeleton such as biphenyl, and other various ultraviolet-ray and electron-beam curable monomers, oligomers and polymers having a carbon-carbon double bond such as vinyl compounds and allyl compounds. But You can use.

More specifically, a bifunctional monomer,
Polyethylene glycol di (meth) as oligomer
Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc .; trifunctional monomer, oligomer, polymer trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate,
Aliphatic tri (meth) acrylate, etc .; tetrafunctional monomers and oligomers include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, aliphatic tetra (meth) acrylate, etc. Examples of the monomer and oligomer include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and (meth) acrylate having a polyester skeleton, a urethane skeleton, and a phosphazene skeleton.

The amount of the above-mentioned monomer or oligomer used is preferably within the range of about 30 parts by weight or less per 100 parts by weight of the binder resin. If the amount of the monomer or oligomer used exceeds the above range, the tack on the surface becomes high and blocking tends to occur, and some material remains on the plate (press stamper) when the hologram is copied (pressed), resulting in repetition. It is not preferable because the embossing property is deteriorated.

Film-like support The film-like support for supporting the layer of the photocurable resin composition used in the sheet of the present invention, particularly in the winding body or the transfer body, includes polyethylene, polypropylene, Ethylene-vinyl acetate copolymer, polyvinyl acetate,
Examples thereof include films of polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polystyrene, polymethyl methacrylate, nylon, polyethylene terephthalate, polyimide, polycarbonate, polynorbornene, triacetyl cellulose and the like.

Release Agent In order to reduce the adhesion of the resin composition to the embossing roller, a release agent may be added to the photocurable resin composition of the present invention.

As the release agent used in the present invention, conventionally known release agents, for example, solid wax such as polyethylene wax, amide wax and polytetrafluoroethylene powder, fluorine-based and phosphoric acid ester-based surfactants,
Any silicone or the like can be used. Particularly preferable releasing agents include modified silicone oil, methylpolysiloxane containing trimethylsiloxysilicic acid, and silicone graft acrylic resin.

Examples of the modified silicone oil include amino modification, epoxy modification, carboxy modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, polyether modification, methylstyryl modification, alkyl modification and fluorine modification. Each is introduced into the side chain and / or the end of the polysiloxane. Two or more of these may be selected and modified.

Among the above silicone oils, the reactive silicone oil of the type having a group reactive with the film-forming component reacts with the resin as the resin layer hardens and binds to the resin. Characteristic performance can be imparted without bleeding out on the surface of the layer. In particular, it is effective in improving the adhesion to the vapor deposition layer in the vapor deposition step.

Photopolymerization Initiator In the present invention, when the photocurable resin composition is cured by ultraviolet rays, it is necessary to add a photopolymerization initiator to the composition, while curing by an electron beam. When it is carried out, the photopolymerization initiator is unnecessary. As the photopolymerization initiator, various photopolymerization initiators used as photopolymerization initiators for conventional UV-curable coatings, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin. Benzoin compounds such as α-phenylbenzoin; anthraquinone compounds such as anthraquinone and methylanthraquinone; benzyl: diacetyl; phenylketone compounds such as acetophenone, benzophenone, 1-hydroxycyclohexylphenylketone; diphenyldisulfide, tetramethylthiuram sulfide, etc. Sulfide compounds; α-chloromethylnaphthalene; halogenated hydrocarbons such as anthracene and hexachlorobutadiene, pentachlorobutadiene, 2-methyl-1-
[4- (Methylthio) phenyl] -2-morpholinopropanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-methyl-1-
Examples include propan 1-one and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Such a photopolymerization initiator is a binder resin 100.
It is preferably used in the range of about 0.5 to 10 parts by weight per part by weight.

Polymerization Inhibitor The photocurable resin composition of the present invention comprises, in addition to the above components, phenols such as hydroquinone, t-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone. Phenothiazines: When a polymerization inhibitor such as copper is added, storage stability is improved.

Solvent The photocurable resin composition of the present invention is used by dissolving it in a suitable organic solvent. As the solvent to be used, any organic solvent can be used as long as each of the composition is soluble,
For example, toluene, aromatic solvents such as xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, methyl cellosolve,
Cellosolve solvent such as ethyl cellosolve, ethyl acetate,
Examples thereof include ester solvents such as butyl acetate and alcohol solvents such as isopropanol. In consideration of coatability, drying property and solvent property, these solvents can be mixed and used as necessary.

Hologram Duplicating Device FIG. 1 shows an example of the configuration of a hologram duplicating device used in the method for forming a fine concavo-convex pattern of the present invention. The hologram duplication device 10 of FIG. 1 includes a pair of main body frames 12 fixed to a bed 13, a paper feeding device 20, a transfer device 30, and an irradiation device 5.
0 and the winding device 60 are sequentially arranged. The paper feeding device 2
At 0, a winding body in which a hologram forming film 1 having a layer of the photocurable resin composition of the present invention formed on a support film is wound around a winding roller 21 is mounted. The transfer device 30 is equipped with a thermocompression bonding roller 40 capable of thermocompression bonding the hologram forming film 1 fed from the paper feeding device 20, and an embossing roller 31 having a hologram original plate provided on the surface thereof. The irradiation device 50 can irradiate the hologram forming film 1 sent from the transfer device 30 with ultraviolet rays or electron beams to cure the hologram layer. The winding device 60 can wind up the hologram sheet with the cured hologram layer.

The embossing roller 31 of the hologram duplicating apparatus 10 is equipped with a press stamper which is subsequently produced from a master hologram produced by using a laser beam. For the press stamper, it is also possible to use a resin plate in which a duplicate hologram is prepared from a master hologram and is stuck on a cylinder.

Light used for exposure As light used for curing the photocurable resin composition of the present invention,
Examples include ionizing radiation such as ultraviolet rays and electron beams. For example,
Electron beam, γ-ray, X-ray, α-ray, neutron, proton beam, etc. radiation accelerated by acceleration of Cockcroft type accelerator, Handegraaf type accelerator, linear accelerator, betatron, cyclotron, ultraviolet fluorescent lamp, low pressure Examples include mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon, carbon arcs, and sun lamps.

Optical article on which a fine concavo-convex pattern is formed The photocurable resin composition (paint) of the present invention is coated on a support such as a polyester film to form a layer of the photocurable resin composition. After forming, after imparting various concave-convex patterns to the layer of the photocurable resin composition by embossing, or while imparting, it is cured by exposing to ionizing radiation of ultraviolet rays or electron beams to form a cured resin layer, and then An optical element for controlling at least one of total light and / or light reflection, transmission, scattering, polarization, light collection or interference of a total light ray and / or a specific wavelength by laminating a metal vapor deposition or a layer having a different refractive index on the formed uneven pattern surface. For example, the optical article of the present invention such as a diffraction grating or a relief hologram can be produced.

Since a hologram is generally a transmission type, it is necessary to provide a layer having a different refractive index as a reflective film on the surface on which the concavo-convex pattern is formed. When a film that reflects light is used as the reflective film, an opaque type hologram is obtained, and when a reflective film having a difference in refractive index from the hologram layer is provided using a transparent substance, it is a transparent type.

The metal thin film used as the reflective film can be formed by a known method such as sublimation, vacuum deposition, sputtering, reactive sputtering, ion plating, electroplating and the like.

As the metal thin film, for example, Cr, Ti,
Fe, Co, Ni, Cu, Au, Ge, Al, Mg, S
b, Pb, Pd, Cd, Bi, Sn, Se, In, G
A thin film formed of a metal such as a or Rb and its oxide, nitride, sulfide or the like alone or in combination of two or more kinds can be used.

It is also possible to form a metal thin film by coating with a high refractive index material. For example, coating with a coating liquid in which a high refractive index filler is dispersed, coating with a colloidal solution of gold or silver, sol gel. Examples include coating film formation by a hydrolysis polycondensation reaction of an organometallic compound represented by a reaction.

In order to produce the optical article of the present invention, it is possible to produce it by using the previously produced sheet, for example, a winding body. Such a winding body is coated with the photocurable resin composition of the present invention on a film-like support, and is dried or not dried, whereby blocking is prevented. The surface of the layer of the uncured photocurable resin composition of the roll is cured by exposure to light after applying various uneven patterns by embossing or while applying the pattern. The optical article of the present invention can be a cured resin layer on which a fine concavo-convex pattern is formed.

Coating and drying using a solvent system which is localized on the surface side of the coating layer during coating and drying is more effective for preventing blocking, and in order to enhance repetitive embossability during replication. Is also effective.

Transfer Foil The release layer used in the layer structure of the transfer foil of the present invention includes an acrylic resin, a polyvinyl chloride resin, a vinyl chloride-vinyl acetate copolymer, a cellulose resin, a silicone resin, a rubber chloride, casein, It is formed by using one kind or a combination of two or more kinds of various surfactants and metal oxides. By providing the peeling layer, when the transfer foil is pressure-bonded to the transfer target, the film-shaped support can be peeled and removed in the peeling layer.

As the adhesive layer used in the layer structure of the transfer foil of the present invention, known adhesives, heat-sensitive adhesives, pressure-sensitive adhesives and curable adhesives can be used. For example,
Examples of heat-sensitive adhesives include rubber-based materials such as polyisoprene rubber, polyisobutylene rubber, and styrene-butadiene rubber, alkyls such as polymethyl (meth) acrylate, polyethyl (meth) acrylate, polypropyl (meth) acrylate, and polybutyl (meth) acrylate. Acrylate-based, polyvinyl ether-based such as polyisobutyl ether, polyamide-based such as polyacrylamide and polymethylolacrylamide, and others, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl butyral, polystyrene, or copolymers thereof. These can be used alone or in combination of two or more.

In the transfer foil of the present invention, the cured resin layer sufficiently adheres to the metal vapor deposition layer in contact with the cured resin layer and the front and rear layers, so that peeling defects such as peeling occur in those layers in contact with the cured resin layer during transfer. It does not occur, and good transfer is possible. Further, since the transfer foil of the present invention has high heat resistance and durability of the transferred product, it is used as an optical element when used for security of credit cards, ID cards, etc., or when information is recorded on holograms. In this case, it is possible to obtain a material that withstands the heat resistance and durability required.

[0086]

[Example] [Example 1] 1. Acrylic resin synthetic condenser In a 2 liter four-necked flask equipped with a dropping funnel and a thermometer, 40 g of toluene and 4 of methyl ethyl ketone
0 g was charged with an azo-based initiator, 2-hydroxyethyl methacrylate 20.8 g, methyl methacrylate 39.0 g, isobornyl methacrylate 45.0.
g, 20 g of toluene, and 20 g of methyl ethyl ketone were added dropwise from a dropping funnel over a period of about 2 hours to react at 100 to 110 ° C. for 8 hours, and then cooled to room temperature. The solid content of the obtained resin solution was 45.0% by weight, and the polystyrene-converted weight average molecular weight was 26000.

2. Preparation of Resin Composition For Composition A and Composition B, the following components were prepared.

Ingredients of Composition A 75 parts by weight of the resin solution (based on solid content) obtained in “1. Synthesis of Acrylic Resin” polyfunctional urethane acrylate (Violet UV-1700B:
Trade name, manufactured by Nippon Synthetic Chemical Industry) 25 parts by weight trimethylsiloxysilicic acid-containing methylpolysiloxane (X-21-5766: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1
Photopolymerization initiator (Irgacure 907: trade name, manufactured by Ciba Specialty Chemicals) 4 parts by weight

Component of Composition B 70 parts by weight of the resin solution (based on solid content) obtained in “1. Synthesis of Acrylic Resin” polyfunctional urethane acrylate (Shikko UV-1700B:
(Trade name, manufactured by Nippon Synthetic Chemical Industry) 30 parts by weight trimethylsiloxysilicic acid-containing methylpolysiloxane (X-21-5766: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1
Photopolymerization initiator (Irgacure 907: trade name, manufactured by Ciba Specialty Chemicals) 4 parts by weight

Preparation of Photocurable Resin Compositions A-1 and B-1
The compositions A and B prepared above were each prepared with methyl ethyl ketone to a solid content of 20% by weight, that is, compositions containing no aluminum coupling agent were designated as photocurable resin compositions A-1 and B-1. .

Preparation of Photocurable Resin Compositions A-2 and B-2
Ltd. The composition A and respectively the aluminum chelate to B (S-75P: trade name, manufactured by Kawaken Fine Chemicals) was added 5% by weight on a solids basis, to prepare a whole solid content of 20 wt% in methyl ethyl ketone, Photocurable resin composition A
-2 and B-2 were obtained.

Preparation of Photocurable Resin Compositions A-3 and B-3
Each aluminum chelate to manufacturing the compositions A and B (ALCH-TR: trade name, manufactured by Kawaken Fine Chemicals)
5% by weight based on the solid content was added, and the whole was adjusted to a solid content of 20% by weight with methyl ethyl ketone to obtain photocurable resin compositions A-3 and B-3.

3. Preparation of film for replication Each of the photocurable resin compositions obtained in the above step was applied to a thickness of 50
A single-sided easy-adhesion-treated polyethylene terephthalate film (Lumirror 50T85S: trade name, manufactured by Toray) having a thickness of μm was coated with a bar coater and dried at 100 ° C., and the film thickness after drying was 2 g / m ² And the film for replication A-1, A-2, A-3, B-1, B-
2 and B-3 were obtained. Each of the obtained reproduction films was non-sticky at room temperature.

4. Blocking test Duplication films A-1, A-2, A produced in the above process
-3, B-1, B-2, and B-3 were loaded on the blocking tester so as to have a load of 5 kg / cm ^2, and stored in an environment of 30 ° C for 24 hours. The film was taken out and confirmed to be rough on the film surface. If the film surface is transparent and does not change, ○, if there is a white shape on the part where the load is applied △, if there is a trace of resin melted out on the part where the load is applied,
When the roughness of the film surface could be confirmed even in the part where no load was applied, it was marked with x. The results are shown in Table 1 below.

According to Table 1, the addition of the aluminum coupling agent has the effect of preventing blocking.

5. Measurement of softening start temperature of photocurable resin composition Each photocurable resin composition B-1, B prepared in the above step 2
-2, B-3, B-4, and B-5 were once raised to 60 ° C. to be softened, and then set on a measuring jig of a dynamic viscoelasticity measuring device. The measurement conditions of the dynamic viscoelasticity measuring method were in accordance with the measuring method described in detail in the section [Means for solving the problem].
The obtained softening start temperature is shown in Table 1 below.

According to Table 1, when the aluminum coupling agent is added in a large amount, the softening temperature is increased, whereas in the aluminum coupling agent added, a large amount is added, the softening temperature is lowered. It can be seen that the low temperature processability is excellent.

6. Observation of film surface of resin sheet Duplication films A-1, A-2, A-3, B-1, B-2, B- obtained in "3. Production of duplication film" above
The surface roughness of the resin layer 3 was measured by an AFM (atomic force microscope) in a tapping mode. The device used for this measurement is Nano Sco manufactured by Digital Instruments.
The pe IIIa type, and the scanning mode was the tapping mode. Scan range is 10μm × 10μm, scan speed is 0.5
The surface roughness average Ra of the unevenness in the depth direction was determined at Hz.

FIG. 2 is a photograph of the AFM image of the duplication film A-1, and FIG. 3 is a photograph of the AFM image of the duplication film A-2.
FIG. 4 shows photographs of AFM images of the duplication film A-3. Ra was 5.904 nm in the duplication film A-1 to which the organometallic coupling agent was not added, whereas the duplication film A-2 to which the organometallic coupling agent was added in an amount of 5% by weight based on the solid content. And A-3, A-2 has Ra of 0.335 nm, and A-3
Then, Ra was 1.304 nm.

From these results, it is recognized that the addition of the organometallic coupling agent enhances the compatibility between the resins and between the resin and the organic solvent to form a uniform film surface.

7. Production of Fine Concavo-Convex Pattern Sheet Next, a press stamper having a fine concavo-convex pattern was set on the embossing roller of the duplication device, the duplication film was set, and heat-pressed to form a fine concavo-convex pattern. The heating conditions are as follows.

(Condition 1) The surface temperature of the press stamper was set to 150 ° C., and press working was performed at a predetermined speed.

(Condition 2) The surface temperature of the press stamper was set to 130 ° C., and press working was performed at a predetermined speed.

(Condition 3) The surface temperature of the press stamper was set to 150 ° C., and press working was performed at a speed twice as fast as the speed of (1). That is, the contact time between the film and the press stamper is 1/2.

After press working, the film was peeled off from the press stamper and irradiated with ultraviolet rays to be cured.

8. Observation of the shape of the fine concavo-convex pattern The surface shape of the fine concavo-convex pattern sheet and the depth of the concavo-convex pattern were compared by tapping mode images of an AFM (atomic force microscope). The images of the surface shapes were visually compared, and those with a regular shape were evaluated as ◯, and those with a rounded shape were evaluated as x. As for the depth of the unevenness, the difference in depth between the deepest part and the shallowest part was obtained. The unevenness depth and the result of shape observation are shown in Table 2 below.

[Embodiment 2] 1. Preparation of high molecular weight type photocurable resin composition The following components were prepared for composition C and composition D.

Ingredients of composition C Polymethylmethacrylate (BR-85: trade name, manufactured by Mitsubishi Rayon, molecular weight 280,000) 75 parts by weight polyfunctional urethane acrylate (Shikoku UV-1700B:
25 parts by weight of trimethylsiloxysilicic acid-containing polymethylsiloxane (X-21-3056: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1
Photopolymerization initiator (Irgacure 907: trade name, manufactured by Ciba Specialty Chemicals) 5 parts by weight

Component of Composition D Polymethylmethacrylate (BR-88: trade name, manufactured by Mitsubishi Rayon, molecular weight 480,000) 70 parts by weight polyfunctional urethane acrylate (Shikko UV-1700B:
Trade name, manufactured by Nippon Synthetic Chemical Industry) 30 parts by weight trimethylsiloxysilicic acid-containing polymethylsiloxane (X-21-3056: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1
Photopolymerization initiator (Irgacure 907: trade name, manufactured by Ciba Specialty Chemicals) 5 parts by weight

Preparation of Photocurable Resin Compositions C-1 and D-1
The compositions C and D prepared above were each prepared with methyl ethyl ketone to a solid content of 10% by weight, that is, the compositions containing no aluminum coupling agent were designated as photocurable resin compositions C-1 and D-1. .

Preparation of Photocurable Resin Compositions C-2 and D-2
Ltd. The compositions C and D each aluminum chelate to (S-75P: trade name, manufactured by Kawaken Fine Chemicals Co., Ltd., having an alkoxy group, a part of it has been chelated) added 5% by weight on a solids basis of Then, the whole was adjusted to a solid content of 10% by weight with methyl ethyl ketone to obtain photocurable resin compositions C-2 and D-2.

Preparation of Photocurable Resin Compositions C-3 and D-3
Ltd. The compositions C and D to each aluminum chelate (ALCH-TR: trade name, manufactured by Kawaken Fine Chemicals Co.,
5% by weight based on the solid content of an alkoxy group having all the alkoxy groups chelated) is added, and the whole is adjusted to 10% by weight with methyl ethyl ketone to prepare a photocurable resin composition C- 3 and D-3 were obtained.

2. Production of film for replication 3. of Example 1 above. Duplicate film C-
1, C-2, C-3, D-1, D-2, D-3 were obtained.

3. Blocking test 4. In the same manner as above, the film for reproduction C-
A blocking test was performed on 1, C-2, C-3, D-1, D-2, and D-3. The results are shown in Table 1 below.

4. 4. Measurement of softening start temperature of photocurable resin composition In the same manner as above, the film for reproduction C-
The softening start temperatures of 1, C-2, C-3, D-1, D-2 and D-3 were measured. The results are shown in Table 1 below.

Table 1 shows that the glass transition temperature after curing is increased by adding the aluminum coupling agent. It can be seen that transferability is improved by adding an aluminum coupling agent.

5. Observation of film surface of resin sheet 6. In the same manner as above, the film for reproduction C-
The film surface was observed for 1, C-2, D-1, and D-2.

As a result, Ra was 0.521 n in the replicating film C-1 containing no organometallic coupling agent.
In contrast, the replication film C-2 containing the organometallic coupling agent in an amount of 5% by weight based on the solid content was Ra.
Was 0.391 nm. Further, in the duplication film D-1 to which the organometallic coupling agent was not added, Ra was 0.620 nm, whereas the duplication film D to which the organometallic coupling agent was added in an amount of 5% by weight based on the solid content. -2 had Ra of 0.427 nm.

6. Preparation of fine uneven pattern sheet 7. In the same manner as above, the film for reproduction C-
The fine concavo-convex pattern sheet was produced about 1, C-2, C-3, D-1, D-2, and D-3.

7. Observation of the shape of the fine concavo-convex pattern 6. Regarding the fine concavo-convex pattern sheet manufactured in [8], The shape of the fine concavo-convex pattern was observed in the same manner as in. The results are shown in Table 2 below.

[0121]

[Table 1]

[0122]

[Table 2]

[0123]

The photo-curable resin composition of the present invention coated on a film-like support is characterized in that blocking is prevented by the organometallic coupling agent in the uncured state before exposure. Further, a sheet having a layer of the photocurable resin composition of the present invention formed on a film-shaped support,
Since the surface becomes smooth, the duplication speed in the fine concavo-convex pattern forming step is increased.

Heat resistance and durability are improved when the photocurable resin composition of the present invention is applied to a film-like support and then the binder resin is cured by exposure. Further, in the case of a layer before and after contact with the cured resin layer, for example, in the case of a transfer foil for forming a relief hologram, the adhesion with the metal vapor deposition layer is improved and the transferability becomes good.

According to the photocurable resin composition of the present invention, even if it is embossed at a relatively low temperature for a relatively short period of time, it is more accurate than the case of using the conventional photocurable resin composition. It is possible to prevent the occurrence of blocking at room temperature in a sheet in which a layer of a photocurable resin composition is formed on a support, for example, a winding body.

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration example of a hologram duplication device used in a method of forming a fine concavo-convex pattern of the present invention.

FIG. 2 is a photograph of an AFM image (atomic force microscope) of the replication film A-1.

FIG. 3 is a photograph of an AFM image (atomic force microscope) of the replication film A-2.

FIG. 4 is a photograph of an AFM image (atomic force microscope) of the replication film A-3.

[Explanation of symbols]

1 Hologram forming film 10 Hologram duplicator 12 body frame 13 beds 20 Paper feeder 21 winding roller 30 transfer device 31 Embossing roller 40 Hot pressing roller 50 irradiation device 60 winding device

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/18 G02B 5/18 5/32 5/32 G03H 1/18 G03H 1/18 1/20 1 / 20 // B29L 11:00 B29L 11:00 C08L 101: 00 C08L 101: 00 F Term (reference) 2H049 AA03 AA07 AA13 AA25 AA40 CA05 CA15 CA22 CA28 CA30 2K008 FF13 FF14 GG01 GG05 4F006 AA02 AA12 AA13 A19 A35 A20 A20 A20 AA36 AA38 AA39 AB24 AB69 BA11 BA12 DA04 4F204 AA21K AD05 AD08 AF01 AG03 AG05 AH73 EA03 EA04 EB02 EB11 EF01 EF23 EK17 EK18 4J027 AB03 AB06 AB07 AB08 BA24 BA15 BA16 BA15 BA07 BA08 BA15 BA07 AG24 BA15 BA27 AG24 AG14 AG27 AG14 AG14 AG15 AG14 AG15 AG14 AG15 AG27 BA26 BA28 CA21 CB10 CC05

Claims (20)

[Claims] 1. A binder resin containing (1) an acrylic resin, (2) a urethane acrylate resin and / or a polyester acrylate resin having a photopolymerizable functional group as essential components, and (3) a composition of the binder resin. A photocurable resin composition containing an organometallic coupling agent for enhancing film property, the photocurable resin composition being used for forming a fine concavo-convex pattern of an optical article. A photocurable resin composition comprising: 2. The organic metal coupling agent is an aluminum coupling agent.
The photocurable resin composition described. 3. The photocurable resin composition according to claim 1, wherein the organometallic coupling agent is 0.1 to 20% by weight based on the total solid content. 4. At least one of the binder resins has a polystyrene-reduced weight average molecular weight of 5,000.
It is a range of -600,000, The photocurable resin composition in any one of Claim 1 thru | or 3 characterized by the above-mentioned. 5. The photocurable resin composition according to claim 1, further comprising a monomer or oligomer having a photopolymerizable functional group. 6. The photocurable resin composition according to claim 1, further comprising a releasing agent. 7. An optical device, characterized by comprising a cured resin layer formed by using the photocurable resin composition according to any one of claims 1 to 6 and having a fine uneven pattern structure on its surface. Goods. 8. A sheet in which the photocurable resin composition according to any one of claims 1 to 6 is applied to a film-like support directly or through another layer and dried or not dried. A sheet that is characterized by being blocked. 9. The sheet according to claim 8, wherein the sheet is a wound body in which the sheet is wound. 10. The photocurable resin composition according to claim 1 is applied to a film-shaped support through a release layer to form a layer of the photocurable resin composition, Further, a transfer foil comprising a photocurable resin composition layer, a layer having a different refractive index, and an adhesive layer in that order. 11. An optical article comprising a cured resin layer formed on the sheet according to claim 8 or 9 by embossing and exposure, the surface having a fine relief pattern structure. 12. The optical article having the fine concavo-convex pattern structure is an optical element for controlling at least one of total light and / or light reflection, transmission, scattering, polarization, condensing or interference of a specific wavelength. Claim 7 or 1 characterized by the above.
1. The optical article according to 1. 13. The optical article according to claim 7, wherein the optical article having the fine concavo-convex pattern structure is selected from a relief hologram, a diffraction grating, an antireflection film, a scattering plate or a reflecting plate. Goods. 14. The optical article having the fine concavo-convex pattern structure is capable of optically recording and / or reading information in the fine concavo-convex pattern structure.
Or the optical article according to item 11. 15. (1) The photocurable resin composition according to any one of claims 1 to 6 is applied to the surface of a film-like support and dried or not dried. (2) The surface of the layer of the photocurable resin composition is subjected to embossing and exposure substantially at the same time to form a cured resin layer having a fine uneven pattern formed on the surface. Method of forming fine concavo-convex pattern. 16. (1) The photocurable resin composition according to any one of claims 1 to 6 is applied to the surface of a film-shaped support and dried or not dried. And (2) embossing the surface of the layer of the photocurable resin composition, and then exposing and curing it to form a fine concavo-convex pattern. 17. A cured resin layer having a fine concavo-convex pattern formed on the surface of the photocurable resin composition layer of the sheet according to claim 8 or 9 by performing embossing and exposure substantially at the same time. And a method for forming a fine concavo-convex pattern. 18. After embossing the surface of the layer of the photocurable resin composition in the sheet according to claim 8 or 9,
A method for forming a fine concavo-convex pattern, which comprises exposing and curing the layer of the photocurable resin composition. (1) A photocurable resin composition according to any one of claims 1 to 6 is applied to a film-like support through a release layer to form a layer of the photocurable resin composition. And (2) embossing and exposing are performed almost at the same time to cure the layer of the photocurable resin composition to form a fine concavo-convex pattern on the surface. (3) Further, to form the photocurable resin composition A layer having a refractive index different from that of the layer, and (4) further forming an adhesive layer to form a transfer foil, and (5) transferring the obtained transfer foil to a transfer target. Manufacturing method. (1) A photocurable resin composition according to any one of claims 1 to 6 is applied to a film-like support through a release layer to form a layer of the photocurable resin composition. And (2) after embossing, it is exposed to cure the layer of the photocurable resin composition to form a fine concavo-convex pattern on the surface. (3) Further, the layer of the photocurable resin composition And (4) further forming an adhesive layer to form a transfer foil, and (5) transferring the obtained transfer foil to a transfer target. Production method.